We length in millimicrons

ABSTRACT

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING COATED THEREON AT LEAST ONE PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER AND IN CONTIGUITY THEREWITH A YELLOW DYEFORMING COUPLER SELECTED FROM THOSE HAVING THE FORMULAS:   Q-CH(-A)-CO-N(-R)-R&#39;&#39;, AND Q-CH(-A)-CO-N(-R)-C6H4-D-W-D&#39;&#39;-   MOIETY OF FORMULA H; A AND A&#39;&#39; EACH REPRESENTS A MEMBER SELECTED FROM THE CLASS CONSISTING OF THE HYDROGEN ATOM, A HALOGEN ATOM AND AN-SB RADICAL; B REPRESENTS A MEMBER SELECTED FROM THE CLASS CONSISTING OF AN ALKYL RADICAL, AN ARYL RADICAL AND A HETEROCYCLIC RADICAL; R AND R&#39;&#39; EACH REPRESENT A MEMBER SELECTED FROM THE CLASS CONSISTING OF THE HYDROGEN ATOM, AN ALKYL RADICAL, AN ARYL RADICAL, AND A HETEROCYLIC RADICAL; D AND D&#39;&#39; EACH REPRESENT A MEMBER SELECTED FROM THE CLASS CONSISTING OF THE   WHEREIN Q AND Q&#39;&#39; EACH REPRESENT A MEMBER HAVING FROM 5 TO 32 CARBON ATOMS SELECTED FROM THE CLASS CONSISTING OF ACYL GROUPS WHEREIN THE CARBON ATOM ATTACHED TO THE CARBONYL RADICAL OF SAID ACYL GROUP IS A TERTIARY CARBON ATOM AND THE SAID CARBONYL RADICAL IS ATTACHED DIRECTLY TO THE CARBON ATOM OF THE ACTIVE METHYLENE IN THE   -CH(-A)-CO-N(-R)-R&#39;&#39;   MOIETY OF FORMULA I AND THE   -CH(-A)-CO-N(-R)-C6H4-D-W-D&#39;&#39;-C6H4-N(-R&#39;&#39;)-CO-CH(-A&#39;&#39;)-     -NH-CO-   GROUP, THE   -CO-NH-   GROUP, THE -NHSO2-GROUP AND THE -SO2NH-GROUP; AND W REPRESENTS A BIVALENT GROUP SELECTED FROM THE CLASS CONSISTING OF A PHENYLENE GROUP AND AN ALKYLENE GROUP. C6H4-N(-R&#39;&#39;)-CO-CH(-A&#39;&#39;)-Q&#39;&#39;

Dec. 25, 1973 WEISSBERGER ETAL 27,848

YELLOW FORMI NG COUPLERS Original Filed May 4, 1964 3 Sheets-Sheet 1 L4Fi g. l

A assonpnou or DYE MADE FROM [.2 W8 (CH3)3 cco CH2 CONHQ NHCO ('IHO QCSH(t) y Cz s 5 A. A5 FORMED m l "FTER H0UR$ EXPOSURE mxEmMART k c. AFTERMoms FADEOMETER 2 06 I Q 7 5 0.6 E

400 20 40 so so 500 20 4o so 600 20 40 6O so 700 '4 WAVELENGIH 0vmum/mom x6 Fi .2

E ABSORPTTON OF DYE MADE FROM (01,9 cco CH2 c0 NH? 0. AS FORMED E. AFTER1 WEEK IN ave/v I40'F, ZSXRH Q r i 1 g o i l a2 1 i 4 400 20 4 0 6050020 40 6O 80 600 20 4O 6O 80 760 WAVELENGTH IN MILLIMICRONS Dec. 25,1973 WESSBERGER 57m Re. 27,848

YELLOW FORMT NU COUITIFR 5 Original Filed May 4, 1964 3 Sheets-Sheet 3"F ABSORPTION F DYE MADE FROM G (CH3)3-CC0 CH2 Q QM" 1.0 mmbo m (11 k F.AS FORMED a G. AFTER 30 nouns sxposunnu moeoneren 2 m 00 Q J q t 2 0v 5Q 0 a4 400 4O 6O 500 20 4O 6O BO 600 20 4O 6O 700 WAVELENGTH INMILLIMICRONS Fl 9. 1 I

ABSORPTIONOF DYE MADE FROM 1.0 ,H c,-,,(u cmcn -cn aocmcmn Q JU g H. AsFORMED m 08 I. AFTER aonouns EXPOSURE m FAOEOMETER Q J I u 06 f h gWAVELENGTH IN MILLIMICRONS DEC. 25, 1973 A. wgssggRggR ET 1 Re. 27,848

YELLOW FORMING COUPI ,BRS

Original Filed May 4, 1964 3 Sheets-Sheet 5 Fig 5 ABSORPTION or DYE MADEFROM C (cmbc-cn mcn corm Qmcflzo J AS FORMED If AFTE R 30 HOURS EXPOSUREIN FADBDMETZ'R OPTICAL DENSITY United States Patent 27,848 YELLOWFORMING CDUPLERS Arnold Weissberger, Rochester, N.Y., and Charles J.Kibler, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester,N.Y.

Original No. 3,265,506, dated Aug. 9, 1966, Ser. No. 364,450, May 4,1964, which is a continuation-in-part of abandoned Ser. No. 25,295, Apr.28, 1960. Application for reissue July 21, 1971, Ser. No. 164,684

Int. Cl. G03c N40 US. Cl. 96-100 15 Claims Matter enclosed in heavybrackets I: II appears in the original patent but forms no part of thisreissue specification; matter printed in italics indicates the additionsmade by reissue.

This is a continuation-in-part application of Weissberger and Kibler US.application Ser. No. 25,295, filed Apr. 28, 1960, now abandoned.

This invention relates to photography and particularly to a new class ofyellow dye forming coupler compounds, and their use in photographicelements for color photography.

The formation of colored photographic images in multilayer elements bycoupling the oxidation products of aromatic amino developing agents withcolor forming or coupling compounds is well known. In these processesthe subtractive process for color formation is ordinarily used and theimage dyes are intended to be of the complementary primary colors, cyanor blue-green, magenta and yellow. The couplers which produce the cyandyes are usually phenols or naphthols, those producing the magenta dyesare ordinarily pyrazolones and those producing the yellow dyes areordinarily compounds containing a methylene group having 2 carbonylgroups attached to it. In multilayer elements for color photography thecyan couplers are usually incorporated in the red sensitive layer, themagenta coupler in the green sensitive layer and the yellow coupler inthe blue sensitive layer. The dyes produced by coupling are azomethine,indoamines or indophenols depending upon the composition of the couplerand of the developer.

It is important that the dyes formed from couplers used in colorphotography have the proper light absorption characteristics. Thus,ideally the yellow dye should have a high absorption for blue light anda low but more or less uniform absorption for green and red light. Thedyes from many of the available couplers do not possess these absorptioncharacteristics to the desired extent. For example, the yellow dyes fromsome of the prior art couplers are an orange yellow because theyabsorbed more green light and less red light than is desired. In orderto use such couplers it has been necessary to increase the red lightabsorption of the resulting dye by mixing a small amount, of the orderof 4-l5%, of a cyan dye forming coupler with the yellow dye formingcoupler and incorporating this mixture in the blue sensitive layer.

The yellow dyes produced from many of the well known couplers are not asstable as is desired.

Many of the known couplers are unstable themselves and when incorporatedin photographic elements are subject to producing discoloration, aneffect called printout when caused by exposure to light over a period oftime or yellowing, an elfect produced by continued exposure of thecoupler to heat. Special processing treatment has been required toreduce the printout and yellowing etiect in photographic emulsionscontaining some prior art couplers. For example, such residual prior artcouplers have been removed from the photographic emulsions afterdevelopment, bleaching and fixing by treatment with water solutions ofvarious alkalis and a water soluble solvent such as methanol,1,2lpropanediol, 1,3-butanediol, 2,3- butanediol, Z-methoxyethanol,ethanol, ethylene glycol,

Re. 27,848 Reissued Dec. 25, 1973 n-propanol, iso-propanol,2-methyl-2,4-pentanediol, betabeta-dihydroxy ethylether,dimethylformamide, propyleneglycol 1,3 ethyleneglycolmonobutylether,diethyleneglycoldiethylether, etc.

It is therefore an object of the present invention to provide a novelclass of yellow dye forming couplers which are especially well suitedfor incorporation in photographic emulsion layers.

Another object is to provide a class of yellow dye forming couplerswhich produce dyes having unusually good light absorptioncharacteristics.

Another object is to provide a novel class of couplers which has goodstability and is not subject to printout and yellowing when incorporatedin photographic elements.

A further object is to provide a novel class of couplers which producedyes of exceptional stability.

Other objects will appear from the following description of ourinvention.

These objects are accomplished according to our invention by the use ofa new class of acetoacetanilide type coupler in which the non-0x0 carbonatom of the aceto group is a tertiary carbon atom. These couplers can beadvantageously represented by the formulas:

and

wherein Q and Q each represent an acyl group having from 5 to 32 carbonatoms in which the carbon atom attached to the carbonyl radical of saidacyl group is a tertiary carbon atom substituted with (a) alkyl radicalshaving 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl,butyl, tert. butyl, amyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl,dodecyl, tridecyl, pe-ntadecyl, hexadecyl, heptadecyl, octadecyl, etc.(provided not more than 2 of said alkyl radicals are secondary ortertiary alkyl radicals), or (b) alkyl radicals which in turn aresubstituted with heteroatoms such as halogen, e.g., chlorine, bromine,iodine, etc., or (c) alkoxy radicals such as methoxy, ethoxy, propoxy,butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, dodecoxy,tridecoxy, pentadecoxy, hexadecoxy, heptadecoxy, octadecoxy, etc., or(d) alkoxyalkyl radicals having from 1 to 18 carbon atoms in which thealkoxy moiety and alkyl moiety are as defined above, for example, andcan be radicals such as methoxymethyl, methoxyoctyl, methoxyheptadecyl,propoxymethyl, propoxyamyl, propoxypentadecyl, hexadecoxyethyl, etc., orthe tertiary carbon atom attached to the carbonyl radical is substitutedas described above but with either 1 or 2 of the (a), (b), (c) or (d)radicals above replaced by (e) an aryl radical, e.g., a phenyl radical,a tolyl radical, etc; or the tertiary carbon attached to the carbonylradical is an integral component of a cycloalkyl radical such as al-alkyl-l-cyclohexyl radical in which the alkyl radical has from 1 to 18carbon atoms as defined above, such as l-methyl-l-cyclohexyl,l-ethyl-l-cyclohexyl, l-propyll -cyclohexyl, l-hexyl-lcyclohexyl,l-octadecyl-l-cyclohexyl, etc., a l-alkoxy-lcyclohexyl radical in whichthe alkoxy radical contains from I to 18 carbon atoms as defined above,such as I-rnethoxy-l-cyclohexyl, l-ethoxy 1 cyclohexyl,l-propoxy-l-cyclohexyl, l-nonoxy-l-cyclohexyl, l-octadecoxyl-cyclohexyl,a l-alkoxyalkyl- 1 -cyclohexyl radical in which the alkoxyalkyl radicalhas from 1 to 18 carbon atoms as defined above, such asl-methoxymethyl-lcyclohexyl, l-rnethoxybutyl-l-cyclohexyl,l-hexadecoxymethyl-l-cyclohexyl, etc., a l-aryl-l-cyclohexyl radicalsuch as l-phenyl-l-cyclohexyl, l-tolyl-l-cyclohexyl, etc., aring-substituted l-alkyl-l-cyclohexyl radical, a substitutedl-alkoxy-l-cyclohexyl radical, a substituted 1- alkoxyalkyl-l-cyclohexylradical as defined above in which the substituerrt is an aryl radicalsuch as phenyl, tolyl, etc., an alkyl radical having from 1 to 12 carbonatoms including those defined above, an alkoxy radical having from 1 to12 carbon atoms including those defined above, such that the acyl groupsQ and Q each have a total of from 8 to 31 carbon atoms; or the tertiarycarbon atom attached to the carbonyl radical is an integral component ofa bicyclic radical, e.g., a terpenyl radical, such as7,7-dimethylnorbornyl, 2-alkyl-7,7-dimethylnorbonyl radicals in whichthe alkyl group has from 1 to 18 carbon atoms as defined above, such as2-methyl-7,7-dimethylnorbornyl, 2-pentadecyl-7,7-dimethylnorbornyl,Z-octadecyl-7,7-dirnethylnorbornyl, etc., a 2-aryl-7,7-dimethylnorbornylradical such as Z-phenyl-7,7-dimethylnorbornyl,2-tolyl-7,7-dimethylnorbornyl, etc., A and A each represents a hydrogenatom, a halogen atom such as chlorine, or bromine, or a SB radical inwhich B is a heterocyclic radical such as 1,3,4-oxadiazolyl,benzoxazole, phenyltetrazolyl, etc., a substituted phenyl radical suchas a 3-alkylcarbamylphenyl in which the alkyl group has from 1 to 18carbon atoms, such as 3-methylcarbamylphenyl, 3-ethylcarbamylpheny1,3-propylcarbamylphenyl, 3-hexylcarbamylphcnyl, 3-decylcarbamylphenyl,3-tetradecylcarbamylphenyl, 3-octadecylcarbamylphenyl, etc., a3-alkyl-4-methoxyphenyl radical, in which the alkyl group has from 1 to18 carbon atoms, such as 3- methyl-4-methoxyphenyl,3-propyl-4-rnethoxyphenyl, 3- nonyl-4-methoxyphenyl, 3-octadecy1 4methoxyphenyl, etc., a dialkyl-4-aminophenyl radical in which the alkylgroups have from 1 to 18 carbon atoms such as2,6-dimethyl-4-aminophenyl, 2,6-diethyl-4-aminophenyl, 2,6-dipropyl-4-aminophenyl, 2,6-dioctyl-4-aminophenyl, 2,6-ditetradecyl-4-aminophenyl, 2,6-dioctadecyl-4-aminophenyl,3,5-dimethyl-4-arninophenyl, 3,5-dipropyl-4-aminophenyl,3,S-didodecyl-4-aminophenyl, etc:; and R and R each represent the sameor a different group, e.g., an aryl group such as phenyl, 2ch1oropheny1,Z-dimethylaminophenyl, etc., a 2-halo-5-alkylamidophenyl radical, e.g.,

Z-chloro-S- [alpha-(2,4-di-tert-amylphenoxy) acetamido] phenyl,

2 chloro-5- alpha- 2,4-di-tert-amylphenoxy) butyramidoJphenyl,

2-chloro-5- alpha- 2,4-di-tert-amylphenoxy amylamidolphenyl,

2-chloro-5 ['y 2,4-di-tert-arnylphenoxy) butyramido] phenyl,

2-chloro-5-(4-methylphenyl sulfonamido)phenyl,

2-fluoro-5-(N-hexylamido)phenyl, etc., a Z-methoXy-S- alkamidophenylradical, e.g.,

Z-methoxy-S- 2,4-di-tert-amylphenoxy) acetamidophenyl,

2-methoxy-5-[alpha-( 2,4-di-tert-amylphenoxy)butyramido]phenyl, etc., a4-alkamidophenyl radical e.g.,

4-(2,4-di-tert-amylphenoxy)acetamidophenyl,

4-['y-(2,4-di-tert-amylphenoxy)butyramidoJphenyl, etc., a

4-methoxyphenyl radical e.g.,

4- N-(v-phenylpropyl )-N-(p-tolyl)carbamylmethoxy] phenyl,

4-[N-(w-phenylhexyl)-N-(p-tolyl)carbamylmethoxy] phenyl, etc., a4-sulfamylphenyl radical, e.g.,

4-[N-( -phenylpropyl )-N-(p-tolyl)sulfamynphenyl,

4-[N-(phenylethyl)-N-(p-toly1)sulfamyl1phenyl, etc., a 2'chloro-S-sulfonamidophenyl radical, e.g.,

2-chloro-5- (p-toluenesulfonamido phenyl,

2-chloro-5-(benzenesulfonamido)phenyl, etc., a 3,5-dicarboxyphenylradical, esters of 3,5-dicarboxyphenyl radicals, e.g.,

3,5-dicarbomethoxyphenyl,

3,4-dicarbohexoxyphenyl,

3 ,S-dicarbododecoxyphenyl,

3,5-dicarbopentodecoxyphenyl,

3,5-dicarbooctadecoxyphenyl, etc., a Z-phenoxy-S-carbamylphenyl radical,e.g.,

2- 2,4-di-tert-amylphenoxy -5- 3 ,5-dicarbomethoxyphenylcarbamyl)phenyl,

2-( 2,4-di-tert-amylphenoxy -5- (N-morpholinocarbonyl) phenyl, etc.,

a 3,5-dicarbamylphenyl radical, etc.;

the hydrogen atom, an alkyl group of 1-18 carbon atoms, e.g., methyl,ethyl, decyl, octadecyl, carboxymethyl, carboxyoctadecyl,carbomethoxyrnethyl, carbobutoxypropyl, beta-hydroxyethyl,-chloropropyl, N-acetamidopropyl, ql-methylcarbamylbutyl,beta-methylsulfonamidoethyl; and a heterocyclic radical selected fromthose of the thiophene series e.g. a 5-carbethoxythiophenyl-(2)-radical, those of the furane series, e.g., a S-carbethoxyfuryl radical,those of the thiazole series, e.g. a 4-methylthiazolyl-(2)-, a4-phenyl-thiazolyl-(2)-, a 4-furyl-thiazolyl-(2)-, a4-methyl-5-carboxyethyl-thiazolyl-(2)-, a 4,5-diphenyl-thiazolyl-(2)-, a4-carboxymethyl-thiazolyl- (2)-, a 4-morp-acylaminophenyl-thiazolyl-(2)-, a 4,5- dicarbethoxy-thiazolyl-(2)-, a4 methyl 5 carbethoxymethylthiazolyl-(2)-, a4-methyl-S-carbethoxythiazolyl- (2)-, a 5-carboxy-thiazolyl-(2)-, a5-carbomethoxythianolyl-(2)-, a 5-carbethoxy-thiazolyl-(2)-, aS-carbethoxy-thiazolyl-(2)- or a benzthiazolyl-(Z)-radical, those of theoxazole series, those of the imidazole series, e.g. abenzimidazyl-(2)-radical, those of the pyridine series, e.g. aS-acylamino-pyridyl-(Z)-, a pyridyl-(4)- or a quinolyl-(2)-radical,those of the 1,3- or 1,4-diazine series, e.g. a2,6-dihydroxy-4-methylpyrimidyl-(5)-radical, those of thel,3,4-thiadiazole series, e.g. aS-carbomethoxyethyl-l,3,4-thiadiazolyl-(2)-radical, those of the1,3,4-0xodiazole series, those of the 1,2,4-triazole series, e.g. a1-(pcarbethoxyphenyl)-3-amino-triazolyl-(5)- or al-(ocarbethoxyphenyl)-3-aminotriazolyl-(5)- or al-(p-carbethoxypheny1)-trioxo1yl-(5) radical and those of the1,3,5-triaziue series; D and D each represent the same or a differentbivalent group such as the O Avai group, the

group, the NHSOggroup, the SO NH- group, etc.; and W represents aphenylene group, e.g., an ophenylene, a p-phenylene or a m-phenylenegroup or an alkylene group having from 1-18 carbon atoms, e.g.,methylene, butylene, decylene, octadecylene, etc.

By tertiary carbon atoms we mean a carbon atom which is in turnconnected to 3 other carbon atoms either directly or through an oxygenatom (as in alkoxy) which are a part of individual radicals, or a carbonatom which is in turn connected to three other carbon atoms which aremembers of cyclic or bicyclic radicals.

Our couplers which have only individual radicals attached to thetertiary carbon atoms can also be represented by the formulas:

Name

Coupler Number 43alpha-pivalyl-alpha-octadecylthio-3,S-dicarboxyacetanilide 44alpha-pivalyl-alpha-(3-octadecylcarbamylphenylthio)-N,N-bis(carboxymethyl acetamide 45alpha-pivalyl-N-(4,5-dicarbethoxy-2-thiazolyl)- acetamide 46N,N-bis[4alpha-pivalylacetamidol-benzenesulfonyl]-hexamethylenediamine 0h h (01131 0 CH NH- SO;ITII

0 l I (CH:):C bemdun-Q-soam IIN in which R and R are as definedpreviously to give a compound of the formula These reactions are usuallycarried out in a suitable solvent, such as, xylene, while the mixture isstirred and refluxed. Compounds of Formulas I and II in which A is otherthan the hydrogen atom are prepared by treating the appropriate compoundof Formula V with an appropriate reagent, e.g., an aryl sulfenyl halideprepared by the reaction of an aryl disulfide or aryl mercaptan with ahalogen; or a heterocyclic sulfenyl halide prepared by reaction of aheterocyclic disulfide or a heterocyclic mercaptan with a halogen,sulfuryl chloride, etc.; an alkyl disulfide or alltyl mercaptan with ahalogen, sulfuryl chloride, etc.

Compounds of Formula IA are prepared to advantage by reacting (l) acompound of Formula I in which R represents an aminophenyl group, achlorosulfonylphenyl group or a chlorocarbonylphenyl group with (2) acompound having the formula:

VI LWL' in which L and L each represents a group, such as the o JLclgroup, the -SO Cl group or the NI-l group and the condensation of twomoles of the compound of Formula I with one mole of LW-L' forms onemolecule of the new coupler and two molecules of HCl. The reaction isconducted in an inert dry solvent such as dry dioxane and in thepresence of a tertiary amine such as triethylamine as an acid acceptor.

Coupler 1 was prepared by the reaction of equirnolar quantities of ethylpivalylacetate and aniline in refluxing xylene (600 mL/mole ofreactants). After a reaction period of 1 hour, the solution was cooled;the product was obtained as coarse white crystals having a M.P. of 77-79C.

Coupler 2 was prepared from ethyl pivalylacetate and 2-chloroaniline bythe procedure described for Coupler l, and was obtained as a solid witha M.P. of 48-50 C.

Coupler 3, prepared from ethyl pivalylacetate and 2-dimethylaminoaniline by the procedure described for Coupler, l, wasobtained as a solid with a M.P. of 68- 70 C.

Coupler 4 was prepared by using the following steps:

Step L-a 2,4-di-tert-amylphenoxy) -4-chloro-3-nitroacetanilide.

To a stirred mixture of 677 g. of anhydrous sodium acetate, 8 liters ofglacial acetic acid, and 448 g. of 4- chloro-3-nitroaniline was added847 g. of (2,4-di-tert-amylphenoxy)-acetyl chloride. The resultingsuspension was stirred for 5 hours at room temperature, then poured into20 liters of water. The solid obtained was recrystallized from alcoholto give 830 g. of white flakes, M.P. 157- 158 C.

Step 2.5 [a-(2,4-di-tert-amylphenoxy -acetamido] -2- chloroaniline.

A solution of 44.6 g. of a-(2,4-di-tert-amylphenoxy)-4-chloro-3-nitroacetanilide in 200 ml. of absolute ethanol was placed ina Parr shaker bottle and hydrogenated at room temperature in thepresence of Raney nickel catalyst. The initial pressure of hydrogen was50 p.s.i., and the reduction was complete in 1 to 1% hours. The mixturewas heated to boiling and filtered, and the filtrate was added to 1500ml. of water. There was thus obtained 32 g. of product, M.P. 117-118 C.

Step 3.--a-pivalyl-5-[a-(2,4 di tert amylphenoxy)- acetamido-2-chloroacetanilide.

To a refluxing solution of 318 g. ofS-[a-ZA-di-tertamylphenoxy)-acetamido]-2-chloroaniline in 2 liters ofxylene was added 125 g. of ethyl pivalylacetate. The mixture was boiledfor 2 hours, during which time ethanol and some xylene were removed bydistillation. The mixture was then filtered into 4 liters of ligroin andcooled; the product thus obtained was recrystallized twice from alcoholto give Coupler 4, M.P. 139-40 C.

Coupler, 5: A stirred solution of 25 g. of Coupler 4 in 150 ml. ofchloroform was cooled in an ice bath, and a solution of 6.48 g. ofsulfuryl chloride in 25 ml. of chloroform was added over a period of V2hour. The mixture was stirred at room temperature for hour, and thesolvent was then removed under vacuum. The residue was recrystallizedtwice from hexane to give 21.3 g. of Coupler 5, M.P. l01-103 C.

Coupler 6 was prepared by the reaction of 4.18 g. of methyla(a'-methoxyisobutyryl)-acetate and 10.0 g. of5-[a-(2,4-di-tert-amylphenoxy)-acetamido] 2 chloroaniline in ml. ofxylene, according to the procedure used for Coupler 4 in Step 3. Therewas thus obtained 9.0 g. of product, which was recrystallized twice froma mixture of hexane and ethanol to give 5.79 g. of Coupler 6, M.P.106109 C.

Coupler 7 was prepared by the reaction of 7.67 g. of5-[u-(2,4di-tert-a.mylphenoxy)-acetamido] 2 chloroaniline and 3.46 g. ofmethyl ut-(methoxypivalyl)-acetate in 50 ml. of xylene, in a mannersimilar to that described for Coupler 4, Step 3. There was thusobtained, after one recrystallization from a mixture of hexane andethanol, 7672 g. of a white crystalline product, M.P. 108- 110 Coupler8, prepared by the reaction of ethyl pivalylacetate with 5[a-2,4-di-tert-amylphenoxy)-acetamido]- 2-chloroaniline according to aprocedure similar to that used for Coupler 4 in Step 3, was obtained asa white solid with a M.P. of 106-108 C.

Coupler 9 was prepared from ethyl pivalylacetate and5-[a'-(2,4-di-tert-amylphenoxy)-butyrarnido] 2 chloroaniline by a methodsimilar to that described for Coupler 4 in Step 3. The product wasrecrystallized from alcohol to give a white solid, M.P. 98.5-l00 C.

Coupler 10 was prepared by the following steps:

Step 1.'y-(2,4-di-tert-amylphenoxy) -4-chloro-3-nitrobutyranilide.

To a stirred mixture of 107.5 g. of anhydrous sodium acetate, 96.0 g. of4-chloro-3-nitroaniline, and 1500 ml.

of glacial acetic acid was added 180 g. of'y-(2,4-di-tertamylphenoxy)-butyryl chloride. The resulting mixture wasstirred at room temperature for hour, permitted to stand overnight, andpoured into 4500 ml. of water. The gummy product was separated, washedwith water and recrystallized twice from methanol to give yellowcrystals, M.P. 86-91 C.

Step 2.-- y- 2,4-di-tert-amylphenoxy -butyramido] 2-chloroaniline.

The reduction of -(2,4-di-tert-amylphenoxy)-4-chloro-S-nitrobutyranilide to5-['y-(2,4-di-tert-amylphenoxy)-butyramido]-2-chloroaniline wasaccomplished in a manner similar to that described for Coupler 4 in Step2. From the hydrogenation of 47.5 g. of the starting nitro compoundthere was obtained, after two recrystallizations from cyclohexane, 36 g.of product, M.P. 113-l15 C.

Step 3.apivalyl-5-['y-(2,4-di-tert-amylphenoxy)-butyramido]-2-chloroacetanilide.

The reaction of 5-['y-(2,4-di-tert-amylphenoxy)-butyramido]-2-chloroaniline and ethyl pivalylacetate in xylene solution was carriedout by a procedure similar to that described for Coupler 4 in Step 3.The product was recrystallized from methanol to give Coupler as a whitesolid, M.P. 55-60 C.

Coupler 11 was prepared from 13.35 g. of 5-[ -(2,4- di tertamylphenoxy)-butyramido]-2-chloroaniline and 5.78 g. of methylu-(chloropivalyD-acetate in 225 ml. of xylene by a procedure similar tothat described for Coupler 4 in Step 3. The crude product wasrecrystallized three times from hexane to give Coupler l1, M.P. 95- 99C.

Coupler 12: The reaction of methyl a-(e'-methoxyisobutyryl)-acetate with5 ['y-2,4-di-tert-amylphenoxy)- butyramido]-2-chloroaniline in xylenesolution was carried out in a manner similar to that described forCoupler 4 in Step 3. The crude product was recrystallized from a mixtureof hexane and ethanol to give the Coupler 12 as a white solid, M.P. 8889C.

Coupler 13: Chlorine gas was passed through a suspension of 8.9 g. of2-mercapto-5-pheny1-1,3,4-oxadiazole in 75 ml. of carbon tetrachlorideuntil complete solution was attained. The solution was evaporated todryness under vacuum and at room temperature, and the residue wasdissolved in 700 ml. of toluene. To this solution was added 22.5 g. ofCoupler 10, and the mixture was heated at 75 C. for 4 hours, thenconcentrated under vacuum and at room temperature. The oily residue wasextracted with methanol, and the extracts were concentrated to a residuewhich was then dissolved in acetic acid. Upon dilution of this solutionwith a large volume of water, the coupler was obtained as a gray-whitesolid M.P. 1101l2 C.

Coupler 14, prepared from equimolar quantities of ethyl pivalylacetateand 4-[N-(' -phenylpropyD-N-(ptolyl)-carbamyl-methoxy]-aniline in amanner similar to that described for Coupler 1, was obtained as a solidhaving a M.P. of 1l8-120 C.

Coupler 15, prepared from ethyl pivalylacetate and 4 [N-('y-phenylpropyl)-N-(p-tolyl)-sulfamyl]-aniline by a method similar tothat used to prepare Coupler 1, was obtained as a solid with a M.P. of158-159 C.

Coupler 16: The reaction of ethyl pivalylacetate with5-p-toluene-sulfoamido-Z-chloroaniline in boiling xylene by a proceduresimilar to that described for Coupler 4 in Step 3 yielded a productwhich was recrystallized from alcohol to give the coupler M.P. 190 192.5C.

Coupler 17: The reaction of 2.0 g. of 2-(2',4-di-tertamylphenoxy)-5- (N-morpholinocarbonyl)-aniline and 1.7 g. of ethyl pivalylacetate in ml.of xylene was carried out in a manner similar to that used for Couplerl. The product was recrystallized from methanol to give 1.5 g. of thecoupler as white crystals, M.P. 178-l80 C.

Coupler 18 was prepared by using the following steps:

Step 1.--e-Pivalyl-3,5-dicarbomethoxyacetanilide.

A mixture of 40 g. of 3,S-dicarbomethoxyaniline, 64 g.

of ethyl pivalylacetate, l g. of anhydrous sodium acetate, and one literof xylene was refluxed for 2 hours. The ethanol which formed was removedby distillation. The mixture was diluted with ligroin, concentrated bydistillation, and cooled to yield 50 g. of product. Recrystallization ofthe product from a mixture of methanol and water yielded material havinga M.P. of -112 C.

Step 2.-To a saturated solution of chlorine in 250 ml. of carbontetrachloride at a temperature of 0-5" C. was added 16.2 g. ofbis-(3-octadecylcarbamylphenyl)-disu1- fide. The mixture was stirred at2535 for 1% hours, then concentrated under vacuum to a yellow residue.This residue was dissolved in 400 ml. of carbon tetrachloride, and tothe solution was added a slurry of 13.4 g. ofa-pivalyl-3,S-dicarbomethoxyacetanilide in 100 ml. of carbontetrachloride. The mixture was heated under re fiux for 2 /2 hours, thencooled to room temperature. The crude product which separated wascollected and recrystallized twice from carbon tetrachloride to give16.8 g. of Coupler 18, M. P. 12l C.

Coupler 19: A slurry of 17 g. of a-pivalyl-3,5-dicarbomethoxyacetanilidein 200 ml. of alcohol was added to a solution of 7 g. of sodiumhydroxide in 100 ml. of water. The mixture was heated at a temperatureof 55-60 C. for 1 hour, then poured into 60 ml. of glacial acetic acid.The crude product obtained on cooling was separated and extracted with amixture of alcohol and ether. The solid obtained by concentration of theextracts was dissolved in alcohol, and this solution was poured into amixture of ice and acetic acid. The coupler was obtained as a whitesolid, M.P. 271.5-2725 C. (dec.).

Coupler 20 was obtained by using the following steps:

Step 1.a-Pivalyl-a- 3-tetradecy1carbamylphenylthio3,5-di-carbomethoxyacetanilide.

This compound was prepared from 11.0 g. of bis-(3-tetradecylcarbamylphenyl)-disulfide and 10.0 g. of c:-pivalyl-3,S-dicarbomethoxyacetanilide by a method similar to thatemployed in the preparation of Coupler 18. The crude product obtainedwas recrystallized from carbon tetrachloride to give 8.5 g. of a whitesolid, M.P. 134- 135 C.

Step 2.e-Pivalyl-u-(3-tetradecy1carbamylphenylthio)-3,5-dicarboxyacetanilide.

A suspension of 4.25 g. ofe-pivalyl-e-(B-tetradecylearbamylphenylthio)-3,S-dicarbomethoxyacetanilidein 40 ml. of ethanol was treated with 4 ml. of 40% aqueous sodiumhydroxide was stirred and heated on a steam bath for 15 minutes. Uponcooling, the mixture was diluted with ethanol and water, then filteredinto dilute hydrochloric acid. There was obtained 3.5 g. of coupler,M.P. -l73 C.

Coupler 21: The reaction of 6.27 g. of di-carbododecyloxyaniline and2.06 g. of methyl pivalylacetate in 45 ml. of xylene in a manner similarto that described for Coupler 4 Step 3, yielded a waxy solid, which wasrecrystallized several times from isopropyl alcohol to give 4.30 g. ofcoupler, M.P. 60-64 C.

Coupler 22 was prepared by using the following steps:

Step l.-3,S-di-carbamylnitrobenzene.

A mixture of 50 g. of S-nitroisophthalic acid and 250 ml. of thionylchloride was heated under reflux overnight. The mixture was concentratedunder vacuum to a solid residue, which was extracted with anhydrousether. The ethereal extract was added dropwise, with stirring, to asolution of anhydrous ammonia in 250 ml. of ether. The product separatedfrom solution and was collected and dried; 28 g. of a colorless solidwas obtained.

Step 2.--3,S-di-carbamylaniline.

A solution of 20 g. of 3,5-di-carbamylnitrobenzene in absolute ethanolwas hydrogenated at room temperature and an initial hydrogen pressure of50 p.s.i. in the presence of palladium on charcoal catalyst. Thecatalyst was removed by filtration, and the filtrate was evaporated toyield 15.8 g. of a tan solid, M.P. 250-253 C. (dec.).

Step 3.a-Pivalyl-3,S-dicarbamylacetanilide.

A solution of 8.0 g. of methyl pivalylacetate was added to a solution of8.8 g. of 3,5-dicarbamylaniline in 500 ml. of xylene containing 0.5 g.of anhydrous sodium acetate. The resulting mixture was refluxedovernight; ml. of distillate was collected during this time. Uponcooling, the coupler was obtained as a colorless solid, M.P. 24l243 C.(dec.).

Coupler 23: 3,5-di-(N-octylcarbamyl)-aniline was prepared byhydrogenation of the product of reaction between S-nitroisophthaloylchloride and n-octylamine; the procedure employed was similar to thatused for Coupler 22 in Steps 1 and 2. Reaction of ethyl pivalylacetatewith 3,5-di-(N-octylcarbamyl)-aniline in xylene solution in a mannersimilar to that described for Coupler 22 in Step 3, yielded Coupler 23,M.P. 88-90 C.

Coupler 24 was obtained by using the following steps:

Step l.-Alpha-pivalyl-4-chlorosulfonylacetanilide.

To 350 ml. of chlorosulfonic acid 44 g. of Coupler l was slowly added;the temperature was maintained below 8 by cooling. The mixture wasstirred, with cooling, for 2 hours after addition was complete. Afterstanding overnight the mixture was poured on ice, and the product whichseparated was extracted with ethyl acetate. The extracts were washedwith water, dried, and concentrated to dryness under vacuum to yield 31g. of a pale yellow solid.

Step 2.-Alpha pivalyl 4 sulfoacetanilide potassium salt.

A solution of one part alpha-pivalyl-4-chlorosulfonyl in 10 parts ofmethanol was refluxed for 3 /2 hours, then filtered and concentratedunder vacuum to dryness. The residue was dissolved in water and treatedwith a saturated aqueous solution of potassium acetate. The solid whichseparated was recrystallized to give Coupler 24 as a whilte solid whichdecomposed without melting at 270 C.

Coupler 25: Alpha-pivalyl-alpha-(3-octadecylcarbamylphenylthio)-4-chlorosulfonylacetanilide was prepared,according to a procedure similar to that described for Coupler 18, from40 g. of bis(3-0ctadecylcarbamylphenyl)- disul fide and 31 g. ofalpha-pivalyl-4-chlorosulfonylacetanilide (prepared as indicated forCoupler 24 in Step 1). The crude product was dissolved in 700 ml. ofmethanol, and the mixture was refluxed for 3 /2 hours, then filtered,concentrated to one-half its original volume, and treated with 10 g. ofpotassium acetate. The solid material which separated was recrystallizedfrom methanol to give Coupler 25 as a white solid.

Coupler 26 may be prepared by the following steps:

Step l.Alpha-(alpha,alpha'-dimethylstearoyl)acetanilide.

Reaction of methyl alpha-(alpha,alpha'-dimethylstearoyl)acetate withaniline in a manner similar to that used to prepare Coupler 1 wouldyield alpha-(alpha',alpha'- dimethylstearoyl acetanilide.

Step 2.Alpha (alpha',alpha' dimethylstearoyl)-4-chlorosulfonylacetanilide.

Treatment of alpha-(alpha',alpha'-dimethylstearoyl)- acetanilideaccording to a procedure similar to that described for Coupler 24 inStep 1, would yield alpha- (alpha,alpha'-dimethylstearoyl) 4chlorosulfonylacetanilide.

Step 3.Alpha (alpha',alpha' dimethylstearoyl)-4- sulfoacetanilidepotassium salt.

Treatment of the chlorosulfonated coupler prepared in Step 2 withmethanol and potassium acetate in a manner similar to that described forCoupler 25 would yield Coupler 26.

Coupler 27 may be prepared from methyl alpha-(alpha',alpha'-di-n-amyl)heptanoylacetate and S-heptanamido-Z- flouraniline by aprocedure similar to that described for Coupler 4 in Step 3.

Coupler 28 was prepared by the following steps:

Step l.Ethyl-7,7-dimethylnorbornanel-carboxylate.

A mixture of 15 g. of 7,7-dimethylnorbornane-l-carboxylic acid (preparedby the method of D. N. Kursanov and S. V. Vitt, Zhur, Obschei Khim., 25,2509 (1955)) and 25 ml. of thionyl chloride was refluxed for 30 minutes.After removal of excess thionyl chloride by distillation under vacuum, asolution of 10 ml. of absolute ethanol in 50 ml. of dry ether was added.The resulting mixture was refluxed for 15 minutes, then cooled, washedwith water, dried over magnesium sulfate, and distilled to give 11 g. ofa colorless liquid, B.P. 103104 C. (18 mm.).

Step 2.7,7-dimethyl-l-cyanoacetylnorbornane.

A solution of 4.1 g. of acetonitrile in 15 ml. of ether was added to asuspension of sodamide (prepared from 2.3 g. of sodium metal) in 200 ml.of liquid ammonia. After 5 minutes a solution of 9.8 g. of ethyl7,7-dimethylnorbornane-l-carboxylate in 15 ml. of ether was added, and,after 30 minutes, 200 ml. of ether was added. The mixture was warmed todrive off excess ammonia, then poured into 500 ml. of water. The aqueousphase was separated, acidified with acetic acid, and extracted withether. The extracts were concentrated, and the residue wasrecrystallized from a mixture of ether and petroleum ether to give awhite solid, M.P. 5860 C.

Step 3.Methyl alpha-(7,7-dimethylnorbornane-l-carbonyl)-acetate.

A solution of 6.0 g. of 7,7-dimethyl-l-cyanoacetylnorbornane in 50 ml.of dry methanol was saturated with hydrogen chloride gas and permittedto stand at room temperature for 15 hours. The mixture was concentratedto dryness under vacuum, and the residue was treated with 35 ml. ofbenzene and 35 ml. of water. The mixture was refluxed for 2 hours; thenthe organic layer was separated, washed with water, and distilled toyield 3.6 g. of a colorless oil, B.P. 10l105 C. (0.3 mm.).

Step 4.-Alpha-(7,7-dimethylnorbornane-l-carbonyl)-3',5-dicarbomethoxyacetanilide.

The reaction of 3.4 g. of methylalpha-(7,7-dimethylnorbornane-1-carbonyl)acetate with 3.1 g. of3,5-dicarbomethoxyaniline in ml. of xylene containing 0.1 g. of sodiumactate was carried out in a manner similar to that described for Coupler18. The product obtained was recrystallized first from ethanol and thenfrom acetonitrile to give 4.5 g. of a white solid with a M.P. of

Step 5.Alpha (7,7-dimethylnorbornane-l-carbonyl)- alpha (3octadecylcarbamylphenylthio)-3,5-dicarbomethoxyacetanilide.

The preparation of this compound from 4.0 g. of alpha7,7-dimethylnorbornane- 1 -carbonyl -3',5'-dicarb0- methoxyacetanilideand 4.05 g. of bisU-octadecylcarbamylphenyUdisulfide was carried out bya procedure similar to that used to prepare Coupler 18. The product wasrecrystallized from carbon tetrachloride to give 5.1 g. of a whitesolid, M.P. l2913l C.

Step 6.Alpha (7,7 dimethylnorbornane-l-carbonyl) alpha(3-octadecylcarbamylphenylthio)-3',5'dicarboxyacetanilide.

A mixture of 4.1 g. of alpha-(7,7-dimethylnorbornane- 1 carbonyl)alpha-(3-octadecylcarbamylphenylthio)-3', 5'-dicarbomethoxyacetanilide,60 ml. of alcohol, and 8.4 ml. of 2 N aqueous sodium hydroxide washeated at 45-50 C. for 45 minutes, then filtered. The filtrate wasacidified with hydrochloric acid, and the material Which separated wasrecrystallized from glacial acetic acid to give 2.5 g. of Coupler 28,M.P. 126-l29 C.

Coupler 29: The reaction of equimolar quantities of methyl alpha(7,7-dimethylnorbornane-I-carbonyl)-acetate (prepared as indicated forCoupler 28 in Steps 1, 2 and 3) and 5-[-(2,4-di-tert-amylphenoxy)butyramido]- Z-chloroaniline (prepared asindicated for Coupler 10 in Steps 1 and 2) was carried out by aprocedure similar to that described in Step 3 for Coupler 4. The productwas recrystallized several times from methanol to give Coupler 29 as awhite crystalline solid, M.P. 99-10l C Coupler 30: The reaction of 13.35g. of 5-['y-(2,4-di tert-amylphenoxy)-butyramido]-2-chloroaniline and6.53 g. of methyl-l-methylcyclohexane-l-carbonylacetate in 100 ml. ofxylene was carried out in a manner similar to that described for Coupler4 in Step 3. The product was recrystallized several times from a mixtureof hexane and ethyl acetate to give 10.5 g. of Coupler 30, M.P. 113-116C.

Coupler 31 was prepared by the following steps:

Step 1.2,5-dichloro-4- (chlorosulfonyl acetanilide.

To 3 liters of chlorosulfonic acid was added 300 g. of3,5-dichlorosulfanilic acid sodium salt with stirring to a temperaturebetween 45 and 50 C. The clear reaction mixture was stirred for one hourat room temperature. After the addition of sulfanilic acid had beencompleted, the mixture was heated on a steam bath overnight. The clearsolution was then added dropwise to crushed ice and the white solidwhich separated was collected, dried, and recrystallized from benzenecyclohexane mixture, yielding 165 g. of product, M.P. 149-151".

Step 2.-2,5 dichloro-4-[N'-(n-octadecyl)-N-methy1- sulfamyl]acetanilide.

To a solution of 440 g. of N-methyl-N-octadecylamine in 4 liters of drypyridine at a temperature of 35 C. was added 470 g. of the product ofStep 1. The mixture was heated to 60 to bring about complete solution,then stirred at room temperature for one hour, after which time it wasdrowned in 40 liters of saturated brine. The solid which separated wascollected and recrystallized from methanol, yielding 520 g. of product,M.P. 74-76 C.

Step 3.-2,5 dichloro-4-[N-(n-octadecyl)-N'-methylsulfamyl]aniline.

To a solution of 388 g. of product of Step 2 in 5 liters of absolutealcohol was added an aqueous solution of 100 g. of sodium hydroxide in200 ml. of water. The resultant clear solution was refluxed for /2 hour,after which time it was cooled under tap water, whereupon a white solidseparated. The mixture was diluted with an equal volume of colddistilled water and left at room temperature overnight. The solid wascollected and recrystallized from 16 liters of methanol, yielding 253 g.of product, M.P. 84-85 C.

Step 4.-A solution of 250 g. of the product of Step 3, 78 g. of methyla-pivalyl acetate, and 0.25 g. of anhydrous sodium acetate in 900 ml. ofdry xylene was refluxed for hours, during which time methanol distilledfrom the mixture. The clear reaction mixture was concentrated in vacuoand the residual glass was then recrystalized from methanol, yielding143 g. of product, M.P. 63-65 C.

Coupler 32 was prepared by the same reactions used to make Coupler 31except that in Step 1 an equivalent amount of 2-chlorosulfanilic acidsodium salt was used in place of 3,5-dichlorosulfanilic acid sodiumsalt. The recrystallized coupler had a M.P. of 75-755" C.

Coupler 33 was prepared by the same reactions used to make Coupler 31except that in Step 1 an equivalent amount of 2-chlorosulfanilic acidsodium salt was used in place of 3,5-dichlorosulfanilic acid sodium saltand in Step 2 an equivalent amount of N-phenyl-N-octadecylamine was usedin place of N-methyl-N-octadecylamine. The recrystallized coupler had aM.P. of 95-97.5 C.

Coupler 34 was prepared by the same reactions used to make Coupler 31excepting that in Step 1 an equivalent amount of Z-chlorosulfanilic acidsodium salt was used in place of 3,5dichlorosuilfanilc acid sodium salt,and in Step 2 an equivalent amount of N-benzyl-N-(l-methyldodecyl)aminewas used in place of N-methyl-N-octadecylamine. The recrystallizedCoupler 34 had a M.P. of 80-81 C.

Coupler 35 was prepared by the same reactions used to make Coupler 31except that in Step 2 an equivalent amount of N-phenyl-N-octadecylaminewas used in place of N-rnethyl-N-octadecylamine. The recrystallizedcoupler had an M.P. of 70-71 C.

Coupler 36 was prepared by the same reactions used to make Coupler 31except that in Step 2 an equivalent amount ofN-benzyl-N-(l-methyldodecyl)amine was used in place ofN-methyl-N-octadecylamine.

Coupler 37 was prepared by the same reactions used to make Coupler 10except that in Step 3 an equivalent amount of ethylu-(a,a-diphenylbutyryl)acetate was used in place of ethylpivalylacetate. The recrystallized coupler obtained had a M.P. of149-155 C.

Coupler 38 was prepared by the same reactions used to make Coupler 10except that in Step 3 an equivalent amount of ethyla-(a-methyl-a-phenyl)propionyl acetate was substituted for ethylpivalylacetate. The recrystallized coupler obtained had an M.P. of 96-98C.

Coupler 39 may be prepared according to a procedure similar to thatdescribed for Coupler 18 but from bis-(3-octadecylcarbamylphenyl)-disulfide and a-(a-phenylisobutyryl) 4chlorosulfonylacetanilide and subsequently forming the potassium saltmonohydrate by refluxing a methanol solution of the crude product,filtering, concentrating the filtrate to one-half its original volumeand treating with potassium acetate as described for Coupler 25, Thea-(a-phenylisobutyryl)-4-chlorosulfonylacetanilide may be prepared bythe reaction used to make Coupler 1 but using ethyla-(a-phenylisobutyryl)acetate in place of ethyl pivalylacetate, and thentreating the product with chlorosulfonic acid as described in thepreparation of Coupler 24.

Coupler 40 may be prepared by reacting 3,5-dicarbomethoxyaniline witha-(a-phenylisobutyryl)acetate, followered by reaction withbis(3-octadecylcarbamylphenyl)- disulfide, then subsequently hydrolyzingthe product with aqueous sodium hydroxide, followed by acidification.

Coupler 41: A mixture of 40 g. of methyl a-pivalylacetate and 47 g. ofdiethylimino acetate in 200 ml. of xylene was refluxed for 1% hours,during which time methanol distilled from the mixture. The resultantsolution Was then concentrated in vacuo and the residual oil wasdistilled (3.1. 146-149 C. at 0.1 ml.), yielding 59 g. of the coupler.

Coupler 42: A mixture of 20 g. of Z-aminothiazol and 33 g. of methyla-pivaliylacetate in 200 ml. of xylene was refluxed for 2% hours, duringwhich time methanol distilled from the mixture. The reaction mixture wasleft at room temperature for 3 days, after which time the solid whichhad separated was collected and recrystallized from a mixture of hexaneand ethyl acetate, yielding 76 g. of product, M.P. 139-143 C.

Coupler 43 may be prepared by a method similar to that used for Coupler20 excepting that dioctadecyl disulfide was used in place ofbis(3-tetradecylcarbamylphenyl)disulfide.

Coupler 44 may be prepared by reacting Coupler 41 withbis-(3-octadecylcarbamylphenyl)-disulfide, followed by alkalinehydrolysis, and finally acidification.

Coupler 45 is prepared by the reactions used to prepare Coupler 42 butsubstituting 2-amino-4,5-dicarbethoxythiazol for Z-aminothiazol.

Coupler 46: To a suspension of 64 g. of m-pivalyl-4- chlorosulfonylacetanilide (prepared in Step 1 of the synthesis of Coupler 24) in 500ml. of dry dioxane at 10 C. was added, with stirring, a solution of 12g. of 1,6-hexanediamine and 61 g. of triethylamine over a period of onehour. The reaction mixture was stirred for an aditional 30 minutes at 10C., after which time the temperature of the mixture was raised to 25 C.over a two hour period. The mixture was heated, stirred at C. for twomore hours, concentrated in vacuo to dryness, and the residue dissolvedin 400 ml. of ethyl acetate. This solution was washed twice with 500 ml.portions of water, dried over magnesium sulfate, and concentrated todryness. The residue was recrystallized twice from methyl alcohol,yielding the product M.P. 98-100" C.

Our couplers are especially adapted for incorporation in light sensitiveemulsion of the developing-out type.

They can be incorporated in photographic emulsions with any of thewell-known coupler solvents, sometimes also known as porosity modifiersor high boiling crystalloidal materials or oil formers of Mannes et al.U.S. Patents 2,304,939 and 2,304,340, and Jelley et al. U.S. Patent2,322,027. Coupler solvent fl-(p-tert-butylphenoxy) ethyl alcohol ofJelley, 2,4-di-tert-amylphenoxyethanol, and other mono-, di-, ortri-alkylphenoxy alcohols can be used to advantage with the couplers ofour invention or with any coupler that is used or can be used with ouremulsions.

Various surfanctants can be used in dispersing agents in preparingcoupler dispersions in gelatin for making photographic emulsions. Thepropylated naphthalenesulfonates such as Alkanol B. Antaron R-275, NekalBX78 and Aerosol US; the sodium alkyl benzenesulfonates such asSul-fon-ate AA-lO, and Nacconal FSNO; sodium lauryl sulfate such asTridupone 51-a; and the N-(carbop-tert-octylphenoxypentethoxy)glutamatesuch as Triglutol-S may be used as dispersing agents for our couplers orfor any coupler that is used in emulsions that are used in photographicproducts with our emulsions.

The emulsions can be chemically sensitized by any of the acceptedprocedures. The emulsions can be digested with naturally active gelatin,or sulfur compounds can be added such as those described in SheppardU.S. Patent 1,574,944, issued March 2, 1926, Sheppard et a1. U.S. Patent1,623,499, issued April 5, 1927, and Sheppared et a1. U.S. Patent2,410,689, issued November 5, 1946.

The emulsions can also be treated with salts of the noble metals such asruthenium, rhodium, palladium, iridium, and platinum. Representativecompounds are ammonium chloropalladate, potassium chloroplatinate, andsodium chloropalladite, which are used for sensitizing in amounts belowthat which produces any substantial fog inhibition, as described inSmith and Trivelli U.S. Patent 2,448,060, issued August 31, 1948, and asantifoggants in higher amounts, as described in Trivelli and Smith U.S.Patents 2,566,245, issued August 28, 1951 and 2,566,263, issued August28, 1951.

The emulsions can be also be chemically sensitized with gold salts asdescribed in Waller et al. U.S. Patent 2,309,083, issued April 23, 1946,and Damschroder et a1. U.S. Patent 2,642,361, issued June 16, 1953.Suitable compounds are potassium chloroaurite, potassiumaurithiocyanate, potassium chloroaurate, auric trichloride and2-aurosulfobenzothiazole methochloride.

The emulsions can also be chemically sensitized with reducing agentssuch as stannous salts (Carroll U.S. Patent 2,487,850, issued November15, 1949), polyamines, such as diethyl triamine (Lowe and Jones U.S.Patent 2,518,- 698, issued August 15, 1950, polyamines, such as spermine(Lowe and Allen U.S. Patent 2,521,925,issued September 12, 1950), orbisQS-aminoethyhsulfide and its water-soluble salts (Lowe and Jones U.S.Patent 2,521,- 926, issued September 12, 1950).

The emulsions can also be optically sensitized with cyanine andmerocyanine dyes, such as those described in Brooker U.S. Patents1,846,301, issued February 23, 1932; 1,846,302, issued February 23,1932; and 1,942,- 854, issued January 9, 1934; White U.S. Patent1,990,507, issued February 12, 1935; Brooker and White U.S. Patents2,112,140, issued March 22, 1938; 2,165,338, issued July 11, 1939;2,493,747 issued January 10, 1950 and 2,739,964, issued March 27, 1956;Brooker and Keyes U.S. Patent 2,493,748, issued January 10, 1950;Sprague U.S. Patents 2,503,776, issued April 11, 1950 and 2,519,- 001,issued August 15, 1950; Heseltine and Brooker U.S. Patent 2,666,761,issued January 19, 1954; Heseltine U.S. Patent 2,734,900, issuedFebruary 14, 1956; Van- Lare U.S. Patent 2,739,149, issued March 20,1956; and Kodak Limited British Patent 450,958, accepted July 15,

The emulsions can also be stabilized with the mercury compounds ofAllen, Byers and Murray U.S. Patent 2,728,663, issued December 27, 1955;Carroll and Murray U.S. Patent 2,728,664, issued December 27, 1955; andLeubner and Murray U.S. Patent 2,728,665, issued December 27, 1955; orwith gold salts as described in Damschroder U.S. Patent 2,597,856,issued May 27, 1952, and Yutz and Leermakers U.S. Patent 2,597,915,issued May 27, 1952', the triazoles of Heimbach and Kelly U.S. Patent2,444,608, issued July 6, 1948; the azaindenes of Heimbach and KellyU.S. Patents 2,444,605 and 2,444,- 606, issued July 6, 1948; HeimbachU.S. Patents 2,444,- 607, issued July 6, 1948 and 2,450,397, issuedSeptember 28, 1948; Heimbach and Clark U.S. Patent 2,444,609, issuedJuly 6, 1948; Allen and Reynolds U.S. Patents 2,713,541, issued July 19,1955 and 2,743,181, issued April 24, 1956; Carroll and Beach U.S. Patent2,716,062, issued August 23, 1955; Allen and Beilfuss U.S. Patent2,735,769, issued February 21, 1956; Reynolds and Sagal U.S. Patent2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164,issued November 27, 1956; and those disclosed by Birr in Z. wiss. Phot.,vol. 47, 1952, pages 2-28; the disulfides of Kodak Belgian Patent569,317, issued July 31, 1958; the quarternary benzothiazolium compoundsof Brooker and Staud U.S. Patent 2,131,038, issued September 27, 1938 orthe polymethylene bisbenziothiazolium salts of Allen and Wilson U.S.Patent 2,694,716, issued November 16, 1954 (e.g.,decamethylene-bis-benzothiazolium perchlorate); or the zinc and cadmiumsalts of Jones U.S. Patent 2,839,405, issued June 17, 1958; and thecarboxyrnethylmercapto compounds of Murray, Reynolds and VanAllen U.S.Patent 2,819,965, issued January 14, 1958.

The emulsions may also contain speed increasing compounds of thequaternary ammonium type of Carroll U.S. Patent 2,271,623, issuedFebruary 3, 1942; Carroll and Allen U.S. Patent 2,228,226, issued June30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November23, 1943; or the quaternary ammonium salts and polyethylene glycols ofPiper U.S. Patent 2,886,437, issued May 12, 1959; and the polyethyleneglycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10,1955; or the thiopolymers of Graham and Sagal U.S. application SerialNo. 779,839, filed December 12, 1958 now U.S. Patent No. 3,046,129, orDann and Chechak U.S. application Serial No. 779,874, filed December 12,1958 now U.S. Patent No. 3,046,134.

The emulsions may contain a suitable gelatin plasticizer such asglycerin; a dihydroxy alkane such as 1,5-pentane diol as described inMilton and Murray U.S. application Serial No. 588,951, filed June 4,1956, now U.S. Patent 2,960,404, issued November 15, 1960; an ester ofan ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) asdescribed in Milton U.S. application Serial No. 662,- 564, filed May 31,1957, now U.S. Patent 2,904,434, issued September 15, 1959; bis(ethoxydiethylene glycol) succinate as described in Gray U.S. applicationSerial No. 604,333, filed August 16, 1956, now U.S. Patent 2,940,854,issued June 14, 1960; or a polymeric hydrosol as results from theemulsion polymerization of a mixture of an amide of an acid of theacrylic acid series, an acrylic acid ester and a styrene-type compoundas described in Tong U.S. Patent 2,852,386, issued September 16, 1958.The plasticizer may be added to the emulsion before or after theaddition of a sensitizing dye, if used.

The emulsions may be hardened with any suitable hardener for gelatinsuch as formaldehyde; a halogensubstituted aliphatic acid such asmucobromic acid as described in White U.S. Patent 2,080,019, issued May11, 1937; a compound having a plurality of acid anhydride groups such as7,8-diphenylbicyclo-(2,2,2)-7-octene- 2,3,5,6-tetra-carboxylicdianhydride, or a dicarboxylic or a disulfonic acid chloride such asterephthaloyl chloride or naphthalene,1,5-disulfonyl chloride asdescribed in Allen and Carroll U.S. Patents 2,725,294 and 2,725,-

295, both issued November 29, 1955; a cyclic 1,2-diketone such ascyclopentane-1,2-dione as described in Allen and Byers U.S. Patent2,725,305, issued November 29, 1955; a bisester of methanesulfonic acidsuch as l,2-di(methanesulfonoxy)ethane as described in Allen and LaaksoU.S. Patent 2,726,162, issued December 6, 1955;1,3-dihydroxymethylbenzimidazol-Z-one as described in July, Knott andPollak U.S. Patent 2,732,316, issued January 24, 1956; a dialdehyde or asodium bisulfite derivative thereof, the aldehyde groups of which areseparated by 2-3 carbon atoms, such as B-methyl glutaraldehyde bissodiumbisulfite as described in Allen and Burness U.S. patent applicationSerial No. 556,031, filed December 29, 1955, abandoned April 21, 1960; abis-aziridine carboxamide such as trimethylene bis(l-aziridinecarboxamide) as described in Allen and Webster U.S. Patent applicationSerial No. 599,891, filed July 25, 1956, now U.S. Patent 2,950,197,issued August 23, 1960; or 2,3- di-hydroxy dioxane as described inJeffreys U.S. Patent 2,870,013, issued January 20, 1959; orbisisocyanate as described in Henn et al. U.S. Patent application SerialNo. 805,357, filed April 10, 1959 now U.S. Patent No. 3,103,437.

The emulsions may contain a coating aid such as saponin; a lauryl oroleyl monoether of polyethylene glycol as described in Knox and DavisU.S. Patent 2,831,766, issued April 22, 1958; a salt of sulfated andalkylated polyethylene glycol other as described in Knox and Davis U.S.Patent 2,719,087, issued September 7, 1955; an acylated alkyl taurinesuch as the sodium salt of N-oleyl-N-methyl taurine as described inKnox, Twardokus and Davis U.S. Patent 2,739,891, issued March 27, 1956;the reaction product of a dianhydride of tetracarboxybutane with anlacohol or an aliphatic amine containing from 8 to 18 carbon atoms whichis treated with a base, for example, the sodium salt of the monoester oftetracarboxybutane as described in Knox, Stenberg and Wilson U.S. Patent2,843,487, issued July 15, 1958; a water-soluble maleopimarate or amixture of a water-soluble maleopimarate and a substituted glutamatesalt das described in Knox and Fowler U.S. Patent 2,823,123, issuedFebruary 11, 1958; an alkali metal salt of a substituted amino acid suchas disodium N- (carbo-p-tert-octylphenoxypentaethoxy)-glutamate asdescribed in Knox and Wilson U.S. patent application Serial No. 600,679,filed July 30, 1956, now U.S. Patent No. 3,038,804; or asulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamate r N-lauryl disodium sulfosuccinamate as described inKnox and Stenberg U.S. patent application Serial No. 691,125, filedOctober 21, 1957, now U.S. Patent 2,992,108, issued July 11, 1961; or asodium salt of an alkylarylpolyether sulfonate of U.S. patentapplication Serial No. 753,642, filed August 7, 1958, now U.S. Patent3,026,202, issued March 20, 1962.

The couplers which we have described may be used in various kinds ofphotographic emulsions. They may be added to the emulsion before orafter any sensitizing dyes which are used. Various silver salts may beused as the sensitive salt, such as, silver bromide, silver iodide,silver chloride, or mixed silver halides such as silver chlorobromide orsilver bromoiodide. The couplers are used in emulsions intended forcolor photography, for example, emulsions containing color-formingcouplers or emulsions to be developed by solutions containing couplersor other color-generating materials, emulsions of the mixed-packet type,such as described in Godowsky U.S. Patent 2,698,794, issued January 4,1955; or emulsions of the mixed-grain type, such as described in Carrolland Hanson U.S. Patent 2,592,243, issued April 8, 1952. The couplers canalso be used in emulsions which form latent images predominantly on thesurface of the silver halide crystal or in emulsions which form latentimages predominantly inside the silver halide crystal,

18 such as those described in Davey and Knott U.S. Patent 2,592,250,issued April 8, 1952.

The couplers may also be used in emulsions intended for use in diffusiontransfer processes which utilize the undeveloped silver halide in thenonimage areas of the negative to form a positive by dissolving theundeveloped silver halide and precipitating it on a receiving layer inclose proximity to the original silver halide emulsion layer. Suchprocesses are described in Rott U.S. Patent 2,352,014, issued June 20,1944, and Land U.S. Patents 2,584,029, issued January 29, 1952;2,698,236, issued December 28, 1954 and 2,543,181, issued February 27,1951; and Yackel et al. U.S. patent application Serial No. 586,705,filed May 23, 1956, now U.S. patent 3,020,155, issued February 6, 1962.They may also be used in color transfer processes which utilize thediflfusion transfer of an imagewise distribution of developer, coupleror dye, from a light-sensitive layer to a second layer, while the twolayers are in close proximity to one another. Color processes of thistype are described in Land U.S. Patents 2,559,643, issued July 10, 1951and 2,698,798, issued January 4, 1955; Land and Rogers Belgian Patents554,933 and 554,934 granted August 12, 1957; International PolaroidBelgian Patents 554,212, granted July 16, 1957 and 554,935, grantedAugust 12, 1957; Yutzy U.S. Patent 2,756,142, granted July 24, 1956 andWhitmore and Mader U.S. patent application Serial No. 734,- 14], filedMay 9, 1958, now US Patent No. 3,075,866. They may also be used inemulsions intended for use in a monobath process such as described inHaist et a1. U.S. Patent 2,875,048, issued February 24, 1959, and inweb-type processes, such as the one described in Tregillus et al. U.S.patent application Serial No. 835,473, filed August 24, 1959, now U.S.Patent No. 3,179,517.

In the preparation of the silver halide dispersions employed forpreparing silver halide emulsions, there may be employed as thedispersing agent for the silver halide in its preparation, gelatin orsome other colloidal material such as colloidal albumin, a cellulosederivative, or a synthetic resin, for instance, a polyvinyl compound.Some colloids which may be used are polyvinyl alcohol or a hydrolyzedpolyvinyl acetate as described in Lowe U.S. Patent 2,286,215, issuedJune 16, 1942; a far hydrolyzed cellulose ester such as celluloseacetate hydrolyzed to an acetyl content of 1926% as described in U.S.Patent 2,327,808 of Lowe and Clark, issued August 24, 1943; awater-soluble ethanolamine cellulose acetate as described in Yutzy U.S.Patent 2,322,085, issued June 15, 1943; a polyacrylamide or an imidizedpolyacrylamide as described in Lowe, Minsk and Kenyon U.S. Patent2,541,474, issued February 13, 1951; zein as described in Lowe U.S.Patent 2,563,791, issued August 7, 1951; a vinyl alcohol polymercontaining urethane carboxylic acid groups of the type described inUnruh and Smith U.S. Patent 2,768,154, issued October 23, 1956; orcontaining cyano-acetyl group such as the vinyl alcohol-vinylcyanoacetate copolymer as described in Unruh, Smith and Priest U.S.Patent 2,808,331, issued October 1, 1957; or a polymeric material whichresults from polymerizing a protein or a saturated acylated protein witha monomer having a vinyl group as described in U.S. Patent 2,852,382, ofIllingsworth, Dann and Gates, issued September 16, 1958.

If desired, compatible mixtures of two or more of these colloids may beemployed for dispersing the silver halide in its preparation.Combinations of these antifoggants, sensitizers, hardeners, etc., may beused.

Photographic emulsions containing our couplers are color developed bydeveloper solutions containing any of the well known primary aromaticamino silver halide developing agents such as the phenylene diaminesincluding the alkylphenylenediamines and the alkyltoluenediamines. Theseare generally used in the salt form such as the hydrochloride orsulfate. The p-aminophenols and their substitution products may also beused where the amino group is substituted. All of the developing agentshave an unsubstituted amino group which enables the oxidation product ofthe developer to couple with the color forming coupler compounds to forma dye image. Typical developers containing these developing agents areas follows:

Developer 1 G. Z-amino-S-diethylaminotoluene hydrochloride 2.5 Sodiumsulfite (anhydrous) 5.0 Sodium carbonate (anhydrous) 20.0 Potassiumbromide 2.0 Water to 1.0 liter.

Developer 2 G. N ethyl 13 methanesulfonamidoethyl-3-methyl-4- aminoaliuesulfate 2.0 Sodium sulfite (anhydrous) 0.6

Sodium carbonate (anhydrous) 30.0 Water to 1.0 liter.

The couplers of our invention such as Couplers 18, 20, 25 and 28 arecapable of reacting with oxidized color developer to form a diffusibledye and are therefore useful in the color diffusion transfer processessuch as disclosed in Whitmore et al. Serial No. 734,141, May 9, 1958,now abandoned, Williams et al. Serial No. 780,710, December 16, 1958,now abandoned. Accordingly, the emulsions having these couplers incontiguity can be exposed and developed to form a diffusible dye imagein the region of development which dye image transfers by diffusion to areception layer.

Our invention is further illustrated by the following specific examplesshowing how our couplers are incorporated in photographic emulsions andthen used to produce yellow dye images having valuable light absorptioncharacteristics for color photography.

EXAMPLE I 25 ml. of a dispersion of 1 g. of Coupler and 0.5 g. ofdi-n'butylphthalate coupler solvent in 2.2 g. of gelatin was mixed with5 ml. of a conventional-medium speed silver bromoiodide emulsion and themixture was coated on a suitably-subbed cellulose acetate support. Afterbeing dried, the coating was exposed under an image and developed inDeveloper 2 to form a negative silver and yellow dye image. The silverimage and the residual silver halide were removed by treatment with aconventional ferricyanide bleach followed by a hypo fixing bath leavinga yellow negative image having a A (i.e. maximum absorption) at awavelength of 444 me, and exhibiting particularly good absorptioncharacteristics.

EXAMPLE II Another film sample-coated with the above emulsion wasexposed and given the same processing, but with Developer 1. The yellowdye image produced also had very desirable absorption characteristicsand a A value of 448 m EXAMPLE III An emulsion coating was made as inExample I but in which 1 g. of Coupler 2 and 2 g. of di-n-butylphthalatewas incorporated instead of Coupler 10. This was exposed and developedwith Developer 1. The dye image produced had a maximum absorption of 444my. and the absorption characteristics shown as Curve D of FIGURE 2 ofthe accompanying drawing.

EXAMPLE IV An emulsion coating was made as in Example I but using 1 g.of Coupler 9 and 0.25 g. of di-n-butylphthalate in place of Coupler 10.This was exposed and developed in Developer 2. After removal of thesilver and residual silver halide by conventional bleaching and fixing,a yellow dye image having a h value of 444 m was produced.

20 EXAMPLE v An emulsion coating was made as in Example I but usingCoupler 6 in place of Coupler 10. This was exposed and processed as inExample I to produce a good yellow dye image having a A value of 438 mp.

EXAMPLE VI Another film sample coated with the emulsion of Example V wasgiven the same processing but with Developer 1. This produced a goodyellow dye image having a 2k value of 442 m EXAMPLE VII Similarly, othercouplers of our invention were incorporated in emulsion layers, exposedto an image and developed to produce yellow dye images having valuablecharacteristics for use in color photography.

The following table lists A values for the dyes produced fromrepresentative couplers of our invention.

TABLE 0 Max. value in m of dye produced in silver halide emulsion layercontaining coupler by color de velopment wlth- Ratio of coupler toCoupler di-nbutylphthalate Developer 1 D eveloper 2 TABLE D Y m. of dyeCoupler in m 18 Dimethyl-fl-hydroxyethyl-v-[octadecylamido] 434 propylammonium dihydrogen phosphate.

l9 .do. 426 25 do 434 do" 438 18 Polya-methylallylamlnoguanldineacetate... :23 4

Cetyl trlmethyl ammonium bromide 423 24 do 430 EXAMPLE VIII A sample ofthe emulsion coating of Example I was compared with a similar coating inwhich the et-benzoyl analogue of our Coupler 4 was used. These filmsamples were compared for printout, by exposing for 30 hours in a XenonArc Fadeometer. The film sample containing our coupler at the end of thetest showed only a 0.5% reduction in transmission as compared to the4.5% reduction shown by the film sample containing the a-benzoylanalogue of our coupler. The film samples were compared for yellowing bystoring for one week at F. and 75% RH. The film sample containing ourcoupler 21 showed no reduction in transmission as compared to a 1%reduction in transmission produced by this treatment in the other filmsample.

The valuable light absorbing properties illustrated in the examplesabove which characterize the dyes produced by color development of ournovel couplers is further illustrated by the spectrophotometric curvesshown by the accompanying drawings, FIGURES 1, 2, 3, 4 and 5.

FIGURES 1, 2 and 3 of the drawings show the spectrophotometric curvesfor the dyes produced by color development of Coupler ii in the emulsionof Example 4, Coupler 2 in the emulsion of Example 3, and Coupler in theemulsion as described in Example 2, respectively. These figuresdemonstrate the high absorption our dyes have for blue light and the lowand uniform absorption they have for green and red light which makesthem very desirable for use in color photography.

Our dyes are not only characterized by having very desirable lightabsorption properties when they are originally formed but they retainthese properties to an unexpected degree after being exposed to heat andlight over a period of time.

Table E below illustrates the stability of dyes from representativecouplers of our invention when they were exposed in a Xenon ArcFadeometer.

TABLE E Dyes produced by color development of an exposed silver halideemulsion layer containing- Decrease in dye density til; Yul.

produced by 30 hours exposure Coupler with Developer in Fadeorneter 4 10. l2 6 1 0. ll 9 2 0. l0 l0 2 0. 12 14 1 0. 12 15 1 0. 10

FIGURE 1 of the drawings further illustrates the good stability of ourdyes to exposure to light. Spectrophotometric curves A, B, and Crepresent the light absorption characteristics of our dye beforeexposure, after 30 hours exposure, and after 50 hours exposure in theFadeometer, respectively showing that only a relatively small amount ofdye fading was produced by this severe test. The basic shape of thecurve is unchanged even after 50 hours of exposure.

FIGURE 3 of the drawings still further illustrates the characteristicstability of dyes from our couplers. Curves F and G were obtained for anemulsion containing the dye from our Coupler l0, a-pivalyi-S-[f-(2,4-tert-amylphenoxy)-butyramido]-2-chloroacetanilide as formed andafter 30 hours exposure in the Xenon Arc Fadeometer. This treatmentcaused the dye to fade only 0.12 density unit.

The excellent stability of the dyes from our couplers is unexpected inview of the relatively poor stability of dyes from coupler analogues ofour couplers. The importance of the tertiary carbon connected to thecarbonyl group of our couplers is illustrated by a comparison of FIGURE3 with FIGURE 4 and with FIGURE 5.

Spectrophotometric curves H and I of FIGURE 4 show the light absorptioncharacteristics of the dye produced in an emulsion made as described inExample 1 but which contained the coupler a(a'-methylbutyryl)-5-{'"-(2,4-ditert-amylphenoxy)-butyramido]-2-chloracetaniiide. This coupleris an isomer of Coupler 10 (used to make the dyes illustrated in FIGURE3) and dilfers from Coupler 10 only in that it has a CI'Ig-CHgC I1--group attached to the carbonyl group in place of a (CH C-- group.

FIGURE 4 shows that 30 hours of exposure to the Xenon Arc Fareometerreduced the dye density by 0.70

22 unit. The corresponding loss in density from our coupler shown inFIGURE 3 was only 0.11 density unit.

Spectrophotometric curves J and K of FIGURE 5 show the light absorptioncharacteristics of the dye produced in an emulsion made as described inExample 1, but which contained the coupler a(8',B'-dimethylbutyryl)-5-[a"-(2,4-ditert-amylphenoxy acetamido)]-2-chloroacetanilide in place of Coupler 10. This coupler differs primarilyfrom Coupler 10 in that it has a CH group separating the tertiary butylgroup from the carbonyl group of the coupler. The comparison betweencurves J and K show that 30 hours exposure in the Fadeometer produced aloss in dye density of 0.4 density unit.

Table F below illustrates the good stability to heat shown by dyes fromrepresentative couplers of our invention.

TABLE F Dyes produced by color development of an exposed silver halideemulsion layer containing Dye desnity change in density units producedby storage for 1 Coupler with Developer week at F. 75% R11.

FIGURE 2 of the drawings further illustrates the good stability of ourdyes to heat. A comparison of curves D and B shows that the dye madefromCoupler 2 in the emulsion of Example 3 was changed very little by oneweeks storage in an oven at 140 F. and 75% RH.

The novel class of yellow dye forming acetamide type couplers of ourinvention are characterized by having a tertiary carbon attacheddirectly to the carbonyl group. The tertiary carbon is substituted withalkyl groups, alkoxy groups, or can be a tertiary carbon in a cyclichydrocarbon, or a bridgehead carbon in a bicyclic hydrocarbon. Ourcouplers are unusually valuable for use in color photography as emulsionincorporated couplers. They exhibit considerably less printout uponprolonged exposure to light and less yellowing, than prior art coupierssuch as the u-benzoyl analogues. The dyes produced upon colordevelopment of our couplers have very desirable absorptioncharacteristics with A values in the range of from 430 to 464 m Thespectrophotometric curves for the dyes are characterized by being sharpcutting with relatively low absorption in the green and red areas of thespectrum. Whereas the stability of our dyes to prolonged exposure tolight is exceptionally good, the dyes produced from couplers differingfrom the couplers of our invention only in that they have a primary orsecondary carbon atom instead of a tertiary carbon atom attached to thecarbonyl group show notably poor light stability under the sameconditions. It is thus apparent that the excellent stability both of ourcouplers and of the dyes derived from them is a consequence of theirunique structural features as described above.

The invention has been described in detail with particular reference topreferred embodiments thereof but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

We claim:

1. A photographic element comprising a support having coated thereon atleast one photographic silver halide emulsion layer and in contiguitytherewith a yellow dyeforming coupler selected from those having theformulas:

I p a -prroN 23 and II a [/R l D l w o R 1') -t Q A! wherein Q and Qeach represent a member having from 5 to 32 carbon atoms selected fromthe class consisting of acyl groups wherein the carbon atom attached tothe carbonyl radical of said acyl group is a tertiary carbon atom andthe said carbonyl radical is attached directly to the carbon atom of theactive methylene in the moiety of Formula I and the group, the NHSOgroup and the S0 NH- group; and W represents a bivalent group selectedfrom the class consisting of a phenylene group and an alkylene group.

2. A photographic element comprising a support having coated thereon atleast one photographic silver halide emulsion layer and in contiguitytherewith a yellow dyeforming coupler selected from those having theformulas:

wherein X represents a member selected from the class consisting ofalkyl radicals having from 1 to 18 carbon atoms, substituted alkylradicals having from 1 to 18 carbon atoms, and alkoxy radicals havingfrom 1 to 18 carbon atoms; Y and Z each represent a member selected fromthe class consisting of primary alkyl radicals, secondary alkyl radicalsand tertiary alkyl radicals in which the alkyl radical has from 1 to 18carbon atoms, such that together X, Y and Z have a total of from 3 to 30carbon atoms, A and A each represents a member selected from the classconsisting of the hydrogen atom; a halogen atom, and an SB radical; Brepresents a member selected from the class consisting of an alkylradical, an aryl radical and a heterocyclic radical; R and R eachrepresent a member selected from the class consisting of the hydrogenatom, an alkyl group, an aryl radical and a heterocyclic radical; D andD each represent a member selected from the class consisting of thegroup, the

group, the NHSO group, and the SO NH- group; and W represents a bivalentgroup selected from the class consisting of a phenylene group and analkylene group.

3. A photographic element comprising a support having coated therein atleast one photographic silver halide emulsion layer and in contiguitytherewith a yellow dyeforming coupler selected from those having theformulas:

i i J-d-( IHCN and O O R Jaw- LN l, wherein J represents a memberselected from the class consisting of cycloalkyl and bicycloalkylradicals such that a tertiary carbon atom in the said I group isattached directly to the carbonyl group of the coupler moiety; A and Aeach represents a member selected from the class consisting of thehydrogen atom, a halogen atom, and an SB radical; B represents a memberselected from the class consisting of an alkyl radical, an aryl radicaland a heterocyclic radical; R and R each represent a member selectedfrom the class consisting of the hydrogen atom, an alkyl group, an arylradical and a heterocyclic radical; D and D each represent a memberselected from the class consisting of the o NII( J- group, the

0 H CNH- group, the NHSO group, and the SO NI-l group; and W representsa bivalent group selected from the class consisting of a phenylene groupand an alkylene group.

4. A silver halide emulsion for color photography containingu-pivalyl-5-[v'-( 2,4 ditert-amylphenoxy)butyramido]2-chloroacetanilide.

5. A silver halide emulsion for color photography containing mpivalyl-5-[ne'-(2,4-di-tert-amylphenoxy)acetamido]2-chloroacetanilide.

6. A silver halide emulsion for color photography containing a(l-methylcyclohexane-l-carbonyl)-5-['y-(2,4di-tert-amylphenoxy)butyramido]2-chloroacetanilide.

7. A silver halide emulsion for color photography containing ua-methoxyisobutyry1[a"-(2,4-di-tert-amylphenoxy)aeetamido]-2-ch1oroacetanilide.

8. A silver halide emulsion for color photography containing a(7,7-dimethylnorbornane-I-carbonyD-S-[y-(Z,4-di-tert-amylphen0xy)butyramido-2-chloroacetanilide.

9. A silver halide emulsion for color photography containing 11pivalyla-(3-octadecylcarbamylphenylthio)-4- sulfoacetanilidc potassiumsalt.

10. A photographic element comprising a support having coated thereon atleast one light-sensitive hydrophilic colloid layer containing silverhalide grains and an acylacetarnide yellow dye forming coupler in whichthe said acyl contains a tertiary carbon attached directly to thecarbonyl group of said acyl group and the said carbonyl group isattached directly to an active methylene group of said coupler.

II. A photographic element comprising a support having coated thereon atleast one photographic silver halide emulsion layer and in contiguitytherewith a yellow dyeforming coupler selected from those having theformula:

wherein Q and Q each represent a member having from 5 to 32 carbon atomsselected from the class consisting of carboxylic acyl groups wherein thecarbon atom attached to the carbonyl radical of said acyl group is atertiary carbon atom and the said carbonyl radical is attached directlyto the carbon atom of the active methylene in the moiety of Formula Iand the moiety of Formula II; A and A each represent a member selectedfrom the class consisting of the hydrogen atom, a halogen atom and an ABradical; B represents a member selected from the class consisting of analkyl a member selected fr m the class consisting of an alkyl radical,an aryl radical and a heterocyclic radical; R and R each represent amember selected from the class consisting of the hydrogen atom, an alkylradical, an aryl radical, and a heterocyclic radical, except that R inFormula I is an aryl radical; D and D each represent a member selectedfrom the class consisting of the group, the

group, the -NHSO group and the -SO NH- group; and W represents abivalent gr up selected from the class consisting of a phenylene groupand an alkylene group.

12. A photographic element comprising a support having coated thereon atleast one photographic silver halide emulsion layer and in contiguitytherewith a yellow dyeforming coupler selected from those having theformulas:

wherein X represents a member selected from the class consisting ofalkyl radicals having from 1 to 18 carbon atoms, substituted alkylradicals having from 1 to 18 carbon atoms, and alkoxy radicals havingfrom I to 18 carbon atoms; Y and Z each represent a member selected fromthe class consisting of primary alkyl radicals, secondary alkyl radicalsand tertiary alkyl radicals in which the alkyl radical has from I to 18carbon atoms, such that, together X, Y and Z have a total of from 3 to30 carbon atoms, A and A each represents a member selected from theclass consisting of the hydrogen atom; a halogen atom, and an -SBradical; B represents a member selected from the class consisting of analkyl radical, an aryl radical and a heterocyc'lic radical; R and R eachrepresent a member selected from the class consisting of the hydrogenatom, an alkyl group, an aryl radical and a heterocyclic radical, exceptthat R in Formula I is an aryl radical, D and D each represent a memberselected from the class consisting of the group, the

o JENK- group, the -NHSO group, and the -SO NH- group, and W representsa bivalent group selected from the class consisting of a phenylene groupand an alkylene group.

13. A photographic element comprising a support having coated therein atleast one photographic silver halide emulsion layer and in contiguitytherewith a yellow dyeforming coupler selected from those having theformulas:

27 wherein J represents a member selected from the class consisting ofcycloalkyl and bicycloalkyl radicals such that a tertiary carbon atom inthe said I group is attached directly to the carbonyl group of thecoupler moiety; A and A each represents a member selected from the classconsisting of the hydrogen atom, a halogen atom, and an SB radical; Brepresents a member selected from the class consisting of an alkylradical, an aryl radical and a heterocyclic radical; R and R eachrepresent member selected from the class consisting of the hydrogenatom, an alkyl group, an aryl radical and a heterocyclic radical, exceptthat R in Formula I is an aryl radical; D and D each represent a memberselected from the class consisting of the group, the

O JENK- group, the NHSO group, and the SOgNH- group; and W represents abivalent group selected from the class consisting of a phenylene groupand an alkylene group.

14. A photographic element comprising a support having coated thereon atleast one light-sensitive hydrophilic colloid layer c ntaining silverhalide grains and an acetoacetoanilide yellow dye forming c upler inwhich the aceto group contains a tertiary carbon attached directly tothe carbonyl of said aceto group and the said carbonyl group is attacheddirectly to an active methylene group of said c upIer.

15. A photographic element comprising a support having coated thereon atleast one photographic silver halide emulsion layer containing a yellowdye-forming coupler having the formula wherein X represents a memberselected fr m the class consisting of alkyl radicals having from 1 to 18carbon atoms, substituted alkyl radicals having from I to 18 carbonatoms, and alkoxy radicals having from 1 to 18 carbon atoms; Y and Zeach represent a member selected from the class consisting of primaryalkyl radicals, secondary alkyl radicals and tertiary alkyl radicals inwhich the alkyl radical has 1 to 18 carbon atoms, such that together, X,Y and Z have a total of from 3 to 30 carbon atoms; A represents a memberselected fr m the class consisting of the hydrogen atom; a halogen atom,and an SB radical wh rein B represents a member selected from the classconsisting of a substituted phenyl and a het'erocyclic group; and Rrepresents a phenyl group.

References Cited The following references, cited by the Examiner, are ofrecord in the patented file of this patent or the original patent.

UNITED STATES PATENTS 2,744,933 5/1956 Ehm 26D-562 2,851,494 9/1958Erhart et a1. 260562 2,425,503 8/1947 Barley 96100 2,652,329 9/1953McCrossen 96-100 FOREIGN PATENTS 980,507 1/1965 Great Britain. 1,439,3343/1962 France.

NORMAN G. TORCHIN, Primary Examiner R. L. SCHILLING, Assistant Examiner

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING COATED THEREON ATLEAST ONE PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER AND IN CONTIGUITYTHEREWITH A YELLOW DYEFORMING COUPLER SELECTED FROM THOSE HAVING THEFORMULAS: